Disazo disulfide dyestuffs



United States Patent 3,225,025 DISAZO DESULFIDE DYESTUFFS Charles G. Jeremias, Newberry, S.C., and Frederick E.

3,225,025 Patented Dec. 21, 1965 azo-disulfide dyestuffs, represented by R, will usually be phenyl, substituted phenyl, naphthyl, or substituted naphthyl, and preferably phenyl for reasons of economy.

The azo coupling component or color body in the azoi f gp ggg ic fi gg;?g g ig iag fiigwg a g 3 5 disulfide dyestutfs, represented by R is an arylide of N0 Drawing! Filed M 1963 Set Noyzm M5 acetoaetic acid. Arylides of acetoacetic acid are well (Claims. 60:17 known, and may be defined as the product resulting from the condensation of acetoacetic ester with an aromatic amine. Several non-limiting examples of arylides of g g gif zg 5 1 1 35 2 222 gq gg z gii g i g ig 10 acetoacetic acid are acetoacetanilide, acetoacet-orthofi methog for fi g Samg y anisidide, acetoacet-meta-xylidide, and acetoacet-orthotol 'd'd The azo-disulfide dyestuffs of the present invention are 5 agzwdisulfide dyestuffs of the present invention y g l li h i gfi gfil g h i g be prepared by diazotizing a diamino disulfide of the T T d f .3 formula H NR-S-S-R-NH wherein R is an aryl gg g z ig gg my Su Sn an 1 15 an 6 or substituted aryl substituent, to form a tetrazo com- The method of the present invention is particularly palm of formula characterized in that the above aZo-disulfide dyestuffs are CI N:N R S S R N:N C1 produced by diazotizing one molecular proportion of a 20 di i di lfid f th f l reacting one molecular proportion of the tetrazo compound so formed with two molecular proportions of an I-I N-RSS-RNH alkaline salt of an arylide of acetoacetic acid at pH 6.5-6.8, and recovering the dyestutl thus formed. wherein R is an aryl or substituted aryl substituent to Several m; and lj iti eXamP1es f the g g gg gg gg g g u rzg i Elisi'ulfide dyestuffs and the methods for making same P 1111 I 1 1 0 row. arylide of acetoacetic acid by reacting said tetrazo compound with an alkaline salt of said arylide of acetoacetic Example I acid.

One of the objects of the present invention is to pro- The j i P i 1S by adding duce azo-disulfide dyestuffs that will provide a bright zi s gfg'sg ygg g zg s gg to 2 Y greenish-yellow shade on cotton and regenerated cellug are lose fibers which shade has not been available in the aZohydrochloric acid at m temPertture wlth Stirring 1mm disulfide dglestufis of the prior art dissolved. The resulting solution is cooled to 0 C. and

Another object of the present invention is to produce held at that temperature While a slight F N azo-disulfide dyestuffs that have superior wash fastness 22 22 21 2 5565236 z sf gg g ggs 5 stlmng after they are applied to cotton and regenerated cellu: A E 6 th ar f of lose fibers, which property has not been present in many n c y 9 am 15 of the azo-disulfide dyestuffs of the prior art. pared In a sgparate i g? by adding of A third object of the present invention is to provide 160% aceto'zlcet'ortho'amsidlqe to 600 of Water at azo-disulfide dyestuffs that may be printed on cotton 50 and dlssolvmg thareln 16 of a 50% aqueous and re enerated cellulose fibers solution of NaOH at room temperature, to form a solu- Cert ain azo-disulfide dyestui-f h been known for tion of the sodium salt of acetoacet-ortho-anisidide. Cool a number of years, but have never gone into commercial 45 the to 5 and add thereto n of sodmm use Among the disadvantages and limitations of prior apetata bufler and thereafter to the bufiered azo -disulfide dyestuffs are the followin tron enough 10% aqueous solution of acetic acid at Most of the known azo-disulfide dyestutfs will not 2 5 temperature to bring the Solution to a PH of make wash fast printings on cellulosic fabrics.

Also, azo-disulfide dyestuffs capable of printing cellu- 50 The i compound 18 coupigd i h arylide of logic fibers a br;ght greenish yellow color are unknown acetoacetic acid as follows. While malntaming the soin the prior art lution of the arylide of acetoacetic acid at 0 C., add

The above disadvantages and limitations have been thereto Slowly Over a period ofols minutes. Wlth overcome by the azodisulfide dyestuffs of the present h maze fompounfl at 0 Conunue to Sm invention as follows W the mixture at 0 C. until coupling 15 completed, e.g.

for about additional minutes. For optimum results, Azo-dlsulfida dyfismfis having the formula the coupling is thus carried out at pH of about 6.5-6.8. Filter the resulting product; wash the resulting solid with water at room temperature; and dry at about wherein R is an aryl or substituted aryl substituent and 60 R is an arylide of acetoacetic acid, may be printed on A quantitative yield of a bright greenish yellow mass cellulosoic fibers by the reduction-oxidation method and (azo-disulfide dyestufi) results, which may be used to provide a bright greenish yellow shade with superior print cotton or regenerated cellulose fibers bright greenwash fastness properties. ish yellow shades of superior wash fastness.

The aryl or substituted aryl substituent in the above The chemical formula of the resulting dyestuff is:

HO CCH3 C-CHa con,

Example II CHsO The dyestutl' has the chemical formula:

B OH 4 Example V This example is the same as Example I above, except 27.2 gms. of 2,4-dimethoxy-5-chlor-acetoacetanilide is substituted for the acetoacet-ortho-anisidide utilized in Example I.

The resulting dyestutf will print cotton and regenerated cellulose bright greenish yellow shades of superior Wash fastness, and has the chemical formula:

OCH;

N ll OCH3 01 01 HO(|7CII3 I HO("3CH: @r JQ H 1-1 50H: 0 CH3 Example 111 30 Example VI CHaO bright, greenish yellow shade with excellent wash fastness is:

Example IV This example is the same as Example I above, except that 30.8 gms. of 3,3-dimethoxy-4:4-diaminodiphenyl- 70 disulfide is substituted for the 4z4'-diaminodiphenyldisulfide utilized in Example I.

The resulting dyestutf prints cotton and regenerated cellulose bright greenish yellow shades of superior Wash fastness, and has the chemical formula:

This example is the same as Example I above, except that 24.2 gms. of 2-methoxy-5-chloro-acetoacetanilide is substituted for the acetoacet-ortho-anisidide utilized in 5 Example I.

The resulting dye may be utilized to print cotton or regenerated cellulose fibers bright greenish yellow shades of superior wash fastness, and has the following chemical formula:

OH OH N ll ELQ Example VII This example is the same as Example I above, except that 34.8 gms. of 4:4-diaminodinaphthyldisulfide is substituted for the 4:4'-diaminodiphenyldisulfide.

The resulting azo-disulfide dyestuif may be used to print 75 cotton and regenerated cellulose fibers bright greenish yellow shades of superior wash fastness, and has the folinvention contain a disulfide linkage (RS-S-R), lowing formula: which should be considered the normal oxidized state OCHa 0011::

Example VIII of the dyestuff. Upon reduction in the steamer, the dye molecule is broken between the sulfur atoms to form two This example is the same as Example I above, except l l R S N +R S Na, in which redu ed that of Y P Y form it penetrates the fibers. The oxidizing agent then disulfide is substituted for the 4:4-diaminodiphenyldisulrestores th e-di lfid dyestufl to th R S R, or fide. normal oxidized state, firmly fixed upon the fibers.

The resulting alo'disulfide dyestllfi y be used to Print Therefore, it will be understood that dyes having the cotton and regenerated cellulose fibers bright yellow shades formula R N=N R S Y h i R i an arylide of superior wash fastness, and has the following formula: of acetoacetic acid, R is an aryl of substituted aryl sub- The azo-disulfide dyestuffs of the present invention may stituent, and Y is a substituent, such as CN or NaO S-, be used to print cotton and regenerated cellulose fibers which upon being hydrolyzed causes cleavage, yielding a by the reduction oxidation method. For example, apply free mercapto group attached to the R substituent, may

to cotton fabric a printing paste consisting of 104 grns. be prepared and are the chemical equivalent of the dyes slfil'ch-tl'agafianth g A di(sodiocarboxymethyl) herein claimed and are intended to be covered by the thiocarbonate reducing agent, 4 gms. dicthylene glyc 4 appended claims, inasmuch as these equivalent dyes form urea, 3 gIIlS- NaOH, and 15 gms. of 20% aqueous the azo-disulfide dyestuif of the present invention (the dispersion of azo-disulfide dyestufi; dry the fabric; steam R S S R form) upon being oxidized on the fibers, the fabric for 2-10 minutes with air free steam at 212- What i l imed i 225 F. to reduce the dyestufi; oxidize the dyestuff by im- 1, A compound of th formula,

mersing the fabric for 15 seconds in an acid-oxidizing bath R containing 1 oz. of glacial acetic acid and 1 oz. of sodium 1 1 bichrornate per gallon of water at 140 F.; scour and dry 40 wherein R is a member selected from the group consisting the fabric. of phenyl and mono-methoxylated phenyl and R is an It is believed that the chemistry of the printing reaction arylide of acetoacetic acid. is as follows. The aZo-disulfide dyestuffs of the present 2. A compound of the formula H0 CH; IIO-C-CII3 I Ili l OCH; 0 CH3 3. A compound of the formula CH3 CH3 5 0 0 H3 0 C 11a 5 0 II |-OH II i N= ss N:N I-I G H H o O 0 0 H3 0 C 113 4. A compound of the formula CH3 CH (J-O11 JO 1r 0 H 0 0 G 1-13 H ON=NC -SS -N=N(|l I-iI i MG L MH, g (i 0 5. A compound of the formula (1H3 $1 3 C-OH C-OH 0 1130 gt 1] 0 0 Ha I FII |-N=N S-S -N=N 1'1 I e-Q t O (References on following page) 7 8 References Cited by the Examiner OTHER REFERENCES UNITED STATES PATENTS Venkataraman, Synthetic Dyes, pages 699700 (1952). 1,973,635 9/1934 Lantz 260178 CHARLES B. PARKER, Primary Examiner. FOREIGN PATENTS 559,784 3/1944 Great Britain. 

1. A COMPOUND OF THE FORMULA 